Mixtures of a diene rubber and a partially hydrogenated furfuryl-ketone product



United States Patent MIXTURES OF A DIENE RUBBER AND A PAR- TIALLYHYDROGENATED FURFURYL-KETONE PRODUCT Mortimer T. Harvey, South Orange,N. J., assignor to Harvel Research Corporation, a corporation of NewJersey No Drawing. Application May 1, 1952, Serial No. 285,539

9 Claims. (Cl. 260-455) This invention relates to novel compositions ofmatter and to methods for preparing them. In one of its more specificaspects, the invention is directed to combining (I) a rubbery materialselected from the group consisting of natural rubber, rubbery polymersof chloroprene, rubbery polymers of butadiene, rubbery copolymers ofbutadiene and styrene, and rubbery copolymers of butadiene andacrylonitrile as well as mixtures of two or more of them with (II) apartially hydrogenated organic reaction product normally liquid at 100C., that is, exhibiting cold flow at 100 C. and selected from the groupconsisting of (a) partially hydrogenated monofurfuryl-ketone, (b)partially hydrogenated 'difurfuryl-ketone, (0) partially hydrogenatedorganic reaction masses, said organic reaction masses beforehydrogenation having a viscosity of at least 50 cp. at 25 C. andproduced by reacting under alkaline conditions furfuraldehyde and aketone having at least two hydrogen atoms on an alpha carbon, (d)partially hydrogenated residual fractions of said reaction masses, saidfractions before hydrogenation obtained by heat distillation of saidreaction masses and measuring by weight at least 60% of said reactionmasses, (e) residual fractions obtained by heat distillation of (c) andmeasuring at least 60% by weight of (c), (f) polymerized productsproduced by polymerizing (a)(e) under acidic conditions, said (a)(d)produced by hydrogenating monofurfuryl-ketone, difurfuryl-ketone, saidorganic reaction masses and residual fractions thereof beforehydrogenating to an extent at least approximately 15% and no more thanapproximately 65% of that necessary to completely partiallyhydrogenating furfuraldehyde-ketone organic reaction products and alsoother novel products by thickening or polymerizing said partiallyhydrogenated furfuraldehyde-ketone organic reaction products underacidic conditions. The methods for producing them are disclosed in mycopending applications 144,594, filed February 16, 1950, and 274,080,filed February 29, 1952, which respectively issued on June 17, 1952, asU. S. Patents 2,600,403 and 2,600,764 and are made part hereof. Theydisclose partially hydrogenated products in both the thickened andunthickened states and methods for preparing them.

The furfuraldehyde-ketone reaction products may be prepared by employingany of the methods known to the art. One method which may be employed inthe preparation of the starting materials is to first produce theunhydrogenated reaction products. For this purpose, the furfuraldehydeand ketone are mixed with each other and then thereto is added aquantity of an alkaline material such as an aqueous solution of sodiumhydroxide, potassium hydroxide, lime or the like, These three componentsare mixed with each other in an autoclave or closed unit and shortlyafter the mixture takes place an exothermic reaction occurs and thepressure within the autoclave will rise. This vigorous reaction is noteasily controlled by ordinary methods, such as by using reacting unitswhich have air vents through the top, because under such conditions manytimes there may be losses of some of the reaction products escapingthrough the air vents. For this reason, an autoclave is recommended asthe reacting unit. After the exothermic reaction has subsided, thereaction is practically complete. In order to assure complete reactionand high yields, the mass in the autoclave is externally heated tomaintain it in the state of boiling for a period of time depending uponthe viscosity desired of the resultant reaction mass, which may varyfrom a thin liquid to a solid at room temperature. Generally, I preferthat the time of boiling is such that the viscosity of the reaction massemployed as a starting material when dehydrated is a liquid, that is, itis pourable at 25 C. and for some purposes at the present time nogreater than approximately 20,000 cp. at 25 C., and in all cases nolower than 50 cp. at 25 C. This reaction provides compounds which aremono and di-furfuryl ketones, having the following formulae H C 0:) R oI z in which x is a whole number selected from the group of l and 2, andR is a ketone lacking two of the hydrogen atoms normally on either oneor both of its alpha carbons. These compounds are produced as a resultof reaction between the furfuraldehyde and ketone wherein two hydorgenatoms on the alpha carbons unite with the oxygen of the furfuraldehydeto split oif water. This reaction also provides an amorphous or resinousmaterial. The quantity of said resinous material present in the reactionmass varies and is dependent upon the time magnitude of boiling of thereaction mass and is approximately 5% or more of the reaction mass byweight and in general measures about 5%60% by weight of the reactionmass.

Reference is hereby made to the United States Patent I 2,363,828 whichissued to me and S. Caplan on November 28, 1944, and particularly tothose examples therein disclosing organic reaction products produced byreacting under alkaline conditions furfuraldehyde and a ketone havingtwo hydrogen atoms on an alpha carbon, and all of those compositions aswell as fractions thereof may be employed as the unhydrogen'atedreaction products herein. The resultant reaction mass or any desiredfraction thereof, some of which are particular compounds and others ofwhich may be the residues or mixtures of two or more of them, may beemployed as the unhydrogenated materials. The unhydrogenated reactionproducts thus include the organic reaction masses, the distillates aswell as the residual fractions which may be obtained by the heatdistillation of the masses, and I prefer that the heat distillation ofthe masses be carried out so that the Weight of the residual fraction isat least 60% and preferably 60-95% by weight of the organic reactionmass. All of said unhydrogenated reaction products may be hydrogenatedin order that at least approximately 15% and no more than of the carbonto carbon double bonds thereof have been saturated with hydrogen.

In the following general example, the resultant reaction productsproduced by the general method heretofore described will betreatedmerely to disclose a general method for hydrogenation, it beingunderstood that any of the other aforesaid compositions may be used inplace thereof.

GENERAL EXAMPLE Said resultant reaction mass may then be renderedsubstantially neutral in any convenient manner. This may e easilyaccomplished by adding thereto the requisite amount of an aqueoussolution of an acidic agent, such as hydrochloric acid, sulphuric acid,lactic acid or the like. Generally it is preferable that the amount ofacidic agent be such as to lower the pH of the mass to a value in therange of 3-7.4 and generally in the range of 3-6.

Following this step, the mass is substantially completely dehydrated.One method for doing this is to heat, preferably under a high vacuum,until all of the water and any unreacted components have beensubstantially completely distilled off.

This completely dehydrated reaction product may then be hydrogenatedonly partially by employing a nickel catalyst, maintaining thetemperature thereof at a value of at least 120 C. and preferably in therange of 120- 250 C. and the pressure thereof at a value of at least 25lbs. per square inch and between 25-250 lbs. per square inch. The nickelemployed may be in a finely divided state and may be coupled with anysuitable carrier such as a hydrogenated vegetable oil, hydrogenatedcardanol, etc.

Briefly, the hydrogenation may be accomplished by adding the requisiteamount of nickel catalyst in the carrier to said dehydratedapproximately neutral reaction product and the mixture is heated whilevacuum is applied and agitated until a uniform mixture has beenobtained. When the temperature of the mix reaches 120 C. the externalsource of heat is removed, hydrogen gas is admitted thereto to provide apressure of 25-250 lbs. per square inch whereupon hydrogenation takesplace and is an exothermic reaction. The addition of the hydrogen iscontinued whereupon the temperature of the mass rises and is maintainedat a level no greater than 250 C. and the pressure is maintained at avalue no greater than 250 lbs. per square inch and generally between30-75 lbs. per square inch. The hydrogen is continuously added under theaforesaid conditions until the amount of added hydrogen is approximately70-340 cubic feet measured at 20 C. and 760 mm. pressure. The hydrogenadded and combined is approximately 15- 65% of the quantity of hydrogennecessary for complete saturation of all the carbon to carbon doublebonds thereof. The hydrogenation is discontinued after the desireddegree of hydrogenation has been attained. Then the hydrogenated mass isallowed to cool to room temperature. By this procedure the reaction massafter hydrogenation is still unsaturated. The carbon to carbon doublebonds of the compounds in said mass and outside of the furane ring havebeen at least 50% saturated with. hydrogen, and may be 50-100% saturatedwith hydrogen with -50% saturation with hydrogen of the carbon to carbondouble bonds in the furane ring.

When the mass to be hydrogenated is of a very high viscosity, forexample, over 20,000 cp. at 25 C., I first dissolved the mass in asolvent, such as a high molecular weight ketone and then hydrogenatedunder the aforesaid conditions.

The partially hydrogenated reaction mass may be polymerized or thickenedunder acidic conditions to provide polymerized products of any desiredviscosity. In this manner, slightly to highly polymerized productshaving unusual stability characteristics may be obtained. Thesepolymerized or thickened products are characterized by when maintainedat 300 F. for 24 hours they are in the substantially infusible state atthe end of that period. In general, these polymers, either of low orhigh molecular weight, may be produced by adding to the hydrogenatedmass or any fraction thereof an acidic catalyst such as sulphuric acid,phosphoric acid, hydrochloric acid, diethyl sulphate, zinc chloride,boron trifluoride, or the like to provide an acidic condition such thatthe pH of the mass is in the range of approximately 2-3.5. In factorypractice the pH of the mass is approximately 3 or slightly below. Suchacidified mass is heated to a temperature of 180 F. or above, andgenerally around 220-350 F. until the polymerization or thickening hasreached the desired degree as evidenced by increasing viscosity which inall cases is at least greater than the viscosity of the hydrogenatedmass at 25 C. before said polymerization or thickening. In all cases, Iprefer that the polymerization be discontinued before the mass, when at100 C. is in the solid state, and in all cases in the practice of thisinvention, the polymerized or thickened hydrogenated products as well asthe unpolymerized or unthickened hydrogenated products are in the liquidcondition at 100 C., that is, they Will exhibit flow at 100 C.

The following Examples 1-7 are given merely to further illustrate themethods for providing some of the starting materials and are not to beconstrued in a limiting sense, all parts being given by weight unlessotherwise specified.

Example 1 Into a one-gallon pail is placed a quantity of sodiumhydroxide weighing 2 lbs. 6 oz. Then there is added thereto sufiicientwater to fill the pail and the sodium hydroxide in the Water is stirreduntil the sodium hydroxide is completely dissolved therein. Then in aMonel metal lined autoclave are placed 40 lbs. of furfuraldehyde and 24lbs. of acetone. This autoclave is preferably provided with a mechanicalmixer or agitator which may be in the nature of a paddle mixer. Thismixture is agitated and while in the state of agitation there is addedthereto about of the volume of said heretofore prepared aqueous solutionof sodium hydroxide. With all the valves of the autoclave closed it willbe noted that an exothermic reaction takes place in a very few minutesafter the addition of the sodium hydroxide solution and the temperatureof the mass continuously agitated by the stirrer will rise toapproximately F. in about three or four minutes. After about 10 minutesthere is added to the mass in said autoclave another charge consistingof 40 lbs. of furfuraldehyde and 24 lbs. of acetone. Then to the mass inthe autoclave there is added a second increment of said sodium hydroxidesolution equal in volume to the first addition. After a few minutes thetemperature of the mass will, due to the exothermic reaction, rise toapproximately -1'70 F. The foregoing steps are repeated four more timesso that the amount of furfuraldehyde and acetone added to the autoclaveare equal to 240 lbs. and 144 lbs. respectively, and all of theinitially prepared aqueous solution of sodium hydroxide has been added.After the last addition of sodium hydroxide the temperature of the masswithin the autoclave will have stabilized to about 195 P. Then the masswithin the autoclave may be heated by means of a steam coil locatedtherein and through a jacket carried thereby to maintain the temperatureof the mass between approximately -190 F. for about 30 minutes in orderto complete the reaction and to obtain high yields. The steam is cut offfrom the coil and jacket and then there is added thereto an aqueoussolution of sulphuric acid in quantities sufficient to render the masspractically neutral. In this instance, there may be added an aqueoussolution of sulphuric acid consisting of 3 lbs. 3 oz. of concentratedsulphuric acid diluted in 6 lbs. 6 oz. of water. Then this mass may beheated for about 5 minutes at a temperature between 175-200 F. tosubstantially completely neutralize the mass. The substantially neutralmass may then be substantially completely dehydrated by heating the sameto a temperature of 220 F. with or without vacuum, yieldingapproximately 300 lbs. of dehydrated substantially neutral materialknown as product A, whose viscosity is 92 cp. at 25 C., and having aspecific gravity at 25 C. of 1.150. When this material, product A, isdistilled at a pressure of approximately .1 mm. of mercury pressure afraction (37%) weighing approximately 110 lbs. comes off at temperaturesin the range of 7085' C. and is hereinafter known as fraction I,apparently essentially monofurfuryl-acetone leaving behind a residualfraction known as product RFA, and a [fraction (47%) measuringapproximately 140 lbs. comes oif in the temperature range of 150-165 C.and hereinafter is known as fraction II. The residue measuringapproximately 50 lbs. is a brittle solid on cooling. Analysis offraction I established a carbon content of 70.30% and hydrogen of 5.48%which corresponds to the carbon and hydrogen values of furfural acetonehaving the following formula:

Analysis of fraction II established a carbon content of 73.07% and ahydrogen content of 4.58% corresponding to the carbon and hydrogenvalues of difurfural acetone having the following formula:

Example 1.4

40 lbs. of product A is placed in a -gallon closed unit equipped with ahigh speed propeller. Then one lb. of a catalyst and carrier combinationcontaining 25% of catalytic nickel dispersed in a hydrogenated vegetableoil is added thereto and the mixture is continuously stirred in order tomaintain a uniform distribution of the components. While in this stateof agitation, the mass is externally heated to a temperature of 120 C.after substantially all the air in the container has been evacuatedtherefrom. Then hydrogen is admitted to provide a pressure of 40 lbs.per square inch. Hydrogen is continuously admitted to the mass andhydrogenation takes place exothermically and now the external source ofheat is removed therefrom. By controlling the speed of addition of thehydrogen to the mass, the temperature is maintained at approximately 200C. and the pressure of approximately 50 lbs. per square inch. Thetemperature during hydrogenation may also be controlled by externalcooling. The hydrogen addition is terminated when no more hydrogen istaken up under these conditions with a period of about 30 minutes. Thequantity of hydrogen taken up in this particular hydrogenation stepapparently due to early poisoning of the catalyst amounted toapproximately 145 cubic feet which corresponds roughly to the quantityof hydrogen required to saturate only the unsaturated carbon to carbonatoms outside of the furane ring.

This hydrogenated product A, hereinafter known as HA is still a thinliquid and may be distilled if desired to provide separate variousfractions thereof. By distilling this hydrogenated product A at 0.3 mm.of mercury pressure a fraction distilled off up to 100 C. and wascollected and amounted to 32%; a second fraction amounting to 41%distilled off and was collected at l20l70 C. That fraction whichdistilled off up to 100 C, is hereinafter known as product HA-l andconsisted essentially of a compound having the following formula:

The second fraction which distilled off at l20-170 C. is hereinafterknown as product HA-Z and consisted essentially of a compound having thefollowing formula:

The residue known as HA3 upon cooling was a brittle black solid.

Exantple 2 By using the same procedure as that set forth in Example 1,and substituting 180 lbs. of methyl ethyl ketone for the 144 lbs. ofacetone, and terminating hydrogen addition when approximately cu. ft. ofhydrogen have been taken up, there may be produced a novel hydrogenatedproduct. This hydrogenated product known as product HB may be distilledto provide fractions HB-l and HB-2 respectively, chiefly consisting ofand a resinous residue HB-3 of more than 5% of the hydrogenated mass.

Example 3 By using the same procedure as that set forth in Example 2,and substituting 240 lbs. of diacetone alcohol for lbs. methyl ethylketone, there may be produced a novel hydrogenated product known as HC.This hydrogenated product HC may be distilled to provide fractions HC-land HC-Z respectively, consisting chiefly of and a resinous residue HC-3of more than 5% of the hydrogenated mass.

Example 4 Following the same procedure as that set forth in Example IAand using fresh catalyst and terminating the hydrogenation afterapproximately 70, 100, 150, 175, 210 and 235 cu. ft. of hydrogen weretaken up in six different 40 lb. batches of product A, I obtainedproducts HD, HE, HF, HG, HH and HI, differing from each other in thedegree of hydrogen saturation.

Example 5 Following the same procedure as that set forth in Example lAand employing fresh catalyst, 235 cu. ft. of hydrogen were taken up in a40 lb. batch of product A. Then the same amount of fresh catalyst, .25lb. powdered nickel, was added thereto and hydrogenation continued untila total of 340 cu. ft. of hydrogen was taken up. This product is knownas product HI.

Example 6 Following the same procedure as that of Example 1A andemploying fraction I of Example 1 in place of prodnot A, andterminatingthe hydrogenation after 1.3 and 1.8 moles proportionately of hydrogenwere taken up by 1 mole proportion of saidfraction, approximately 95 and130 cu. ft. of'hydrogen per 40 lbs. of" fraction I. The hydrogenationabove the 1.3. mole proportion proceeded with difficulty. These twohydrogenated products are HK and HL and were respectively about 43% and60% hydrogenated at the carbon to carbon double bonds.

Example 7 Following the same procedure as that of Example 1A andemploying fraction II of Example 1 in place of product A, and 1 to 4moles of hydrogen were taken up. Above 2 moles of hydrogen addition,additional increments of nickel catalyst were used. Various samples of.

1, 2, 3 and 4 moles of hydrogen-addition products are known as HM, HN;HO andHP respectively, and respectively were approximately 15, 30, 50and 65% hydrogen saturated at the carbon to carbon double bonds.

All of these various partially hydrogenated products, examples of whichhave been hereinbefore set forth, may be polymerized or thickened in themanner heretofore generally described to provide polymers thereof andhaving a viscosity at 25 C. at least 100% greater than the partiallyhydrogenated products before saidpolymerization under acidic conditions.

The method which I have employed for ascertaining the pH of the variousmaterials herein is that commonly used in the art for materials that aresubstantially free of water and substantially insolublein water, and isas follows: About a l-20 cc. sample of the material, and in this casethe partially hydrogenated product together with the acidic agent,whosepH is to be ascertained is placed in a test tube containing aboutan equal volume of distilled water. ing while being shaken and thenallowed to stand and come to room temperature. Then this aqueous mass istested with a pH test paper. commonly employed in the art.

According to this invention, said partially hydrogenatedfurfuraldehyde-ketone reaction products, illustrative examples of whichare products HA, HA1, I-IA-2, HB, I-IB-l, HB-Z, I-IC, HC1, HC-Z, andHD-HP, as well as any of them polymerized or thickened under acidicconditions, may be combined with any one or a combination of two or moreof said rubbery materials in the proportions heretofore set forth.

Employing the milling procedures well known to the art, 100 parts byweight of any one or a combination of two or more of said rubberymaterials is milled on a rubber mill. After the rubbery material hasbeen sufficiently broken down by the milling action, there is addedthereto 5-100 parts by weight of any one or a combination of two or moreof said products (II). However, I prefer that when product II is of lowviscosity that the ratio by weight of the rubbery material to product llbe 100 parts of the former to 550 parts of the latter, because of thestrength of the combined materials on the mill; but when product II isof high viscosity then the ratioby weight of the rubbery material toproduct. II may be 100 of the former to 5-100 of the latter. Instead ofemploying a rubber mill to effect the combination, the combination maybe produced by employing any one of a variety of mixers such as doughmixers, Banbury mixers, etc., and in such cases the quantity of fillersand other components maybe so adjusted that 5-100 parts of product IImay be intimately combined with 100 parts of the rubbery materialwhatever the viscosity of product II. By whatever method and apparatusemployed, said rubbery material andproduct II may also be combined withsuitable fillers, vulcanizers, etc., to provide a homogeneous mass. Thesequence of blending the fillers, vulcanizers, and product II may vary.After the blendedrnass has been.prodi1ced, it may be extruded, moldedorotherwise formed'andcured'according The mixture is heated to aboutboil-- to theendproductdesired. For, example, the composition may beextruded directly on to-a cable or other conductor andsuchcovering-thereon may be subsequently cured to provide insulation ofhigh dielectric strength and ozone resistance.

The'following examples are given merely to illustrate only some of thenovel compositions of this invention and are not to be construed in alimiting sense, all parts being given by weight unless otherwiseindicated.

EXAMPLE A operation, the mass is substantially homogeneous and isnowstripped from the mill. This resultant mass may be extruded, molded orin another manner formed and subsequently cured at 275-325 C. for aperiod of 60-5 minutes.

EXAMPLE B parts of HycarOR-25 (copolymer of butadiene and acrylonitrile)was broken down on the mill and there was successively blended therewiththe following components: 1 part of stearic acid, 60 parts of SRF Black(carbon black), 5-100 parts of product HA, 2 parts of sulphur, and 1.5parts of benzothiazyl disulphide. At the end of this blending operation,the same subsequent procedure is followed as in Example A to provide awide variety of novel products.

EXAMPLE C 100 parts of GRS-SP 65 (copolymer of butadiene and styrene) isplaced on a rubbery mill and there was successively blended therewiththe following components: 1 part of stearic acid, 50 parts of SRF Black,5-30 parts of productHA, 1 part of phenyl beta naphthylamine, 2 parts ofsulphur, 1.5 parts of mercapto benzo thiazole and 0.15 part of zincdimethyl dithio carbamate. At the end of-thisblending operation, thesame subsequent procedure is followed as in Example A to provide a widevariety of novel products.

EXAMPLE D 100 parts of natural rubber (smoked sheet) is placed on arubber mil], broken down and there is blended therewith the followingcomponents: 1 part of stearic acid, 0.5 part ofphenyl betanaphthylamine, 4 parts zinc oxide, 75 parts Dixie clay, 5-50 partsproduct HA, 20 parts litharge, 3 parts sulphur, and 1.5 partsbenzothiazole disulphide. At the end of this blending operation, thesame subsequent procedure is followed as in Example A to provide a widevariety of novel products.

EXAMPLE E Employing the same procedure and materials as set forth inExamples AD, but for HA substituting the products HA-l, HA-Z, HB, HB-1,HB-2, HC, HC-l, HC2, or HD-I-IP, or any one of them or HA polymerizedunder acidic conditions and at 100 C. having a viscosity at least twicethat of the product before said acid polymerization and all being theliquid state at that temperature, a number of highly useful products areobtained.

Examples of other ketones which may be employed to produce the startingmaterials employed herein are methyl isobutyl ketone, isophorone,cyclohexanone, mesityl oxide, methyl n-arnyl ketone, acetonylacetone,diethyl ketone, di-isobutyl ketone, etc.

Since certain changes in carrying out the aforesaid processes andcertain modifications in the compositions which embody the invention maybe made without departing from itsscope, it is intended that all matterconand not in a limiting sense.

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed and all statements of the scope of the invention, which as amatter of language might be said to fall therebetween; and that they areintended to be inclusive in scope and not exclusive, in that, ifdesired, other materials may be added to my novel composition of matterherein claimed without departing from the spirit of the invention.Particularly it is to be understood that in said claims, ingredients orcomponents recited in the singular are intended to include compatiblemixtures of said ingredients wherever the sense permits.

This application is a continuation in part of my pending applicationsSerial No. 732,124 of March 3, 1947; Serial No. 740,742 of April 9,1947; subsequently abandoned and Serial No. 144,594 of February 9, 1950,and Serial No. 274,080 of February 29, 1952, respectively issued as U.S. Patents 2,600,403 and 2,600,764 on June 17, 1952.

I claim:

1. A composition of matter comprising (I) a material selected from thegroup consisting of natural rubber, rubbery polymers of chloroprene,rubbery homopolymers of butadiene, rubbery copolymers of butadiene andstyrene, rubbery copolymers of butadiene and acrylonitrile intimatelycombined with (II) a partially hydrogenated organic reaction productnormally liquid at 100 C. and selected from the group consisting of (a)partially hydrogenated monofurfuryl-ketone, (b) partially hydrogenateddifurfuryhketone, (c) partially hydrogenated organic reaction masses,said (c) being (x) organic reaction masses having a viscosity of atleast 50 centipoises at 25 C. and produced by reacting under alkalineconditions furfural and a ketone having at least 2 hydrogen atoms on analpha carbon and then hydrogenating (x) by combining hydrogen therewithto an extent at least approximately and no more than approximately 65%of that necessary to completely saturate with hydrogen the carbon tocarbon double bonds thereof, (d) partially hydrogenated residualfractions of (x), said (d) being residual fractions of (x) obtained bythe heat distillation of (x) and measuring at least 60% of the weight of(x) and then hydrogenating said residual fractions of (x) by combininghydrogen therewith to an extent at least approximately 15% and no morethan approximately 65 of that necessary to completely saturate withhydrogen the carbon to carbon double bonds thereof, (:2) residualfractions of (0) obtained by the heat distillation of (c) and measuringat least 60% by weight of (c), (f) polymerized products produced bypolymerizing (a)-(e) respectively under acidic conditions, said (a) and(b) respectively produced by hydrogenating monofurfuryl-ketone anddifurfuryl ketone by combining hydrogen therewith to an extent at leastapproximately 15% and no more than approximately 65 of that necessary tocompletely saturate with hydrogen the carbon to carbon double bondsthereof the ratio by weight of (II) to (I) being no greater than 100 to100.

2. A composition of matter comprising (I) a rubbery material selectedfrom the group consisting of natural rubber, rubbery polymers ofbutadiene, rubbery homopolymers of chloroprene, rubbery copolymers ofbutadiene and styrene, and rubbery copolymers of butadiene andacrylonitrile intimately combined with (H) a partially hydrogenatedorganic reaction mass normally liquid at 100 C. said (II) being (x) anorganic reaction mass having a viscosity of at least 50 centipoises at25 C. and

, produced by reacting under alkaline conditions furfural and a ketonehaving at least 2 hydrogen atoms on an alpha carbon and thenhydrogenating (x) by combining hydrogen therewith to an extent at leastapproximately 15 and no more than approximately 65% of that necessary tocompletely saturate with hydrogen the carbon to 10 carbon double bondsthereof the ratio by weight of (II) to (I) being no greater than to 100.

3. A composition of matter comprising (1) a rubbery material selectedfrom the group consisting of natural rubber, rubbery polymers ofchloroprene, rubbery homopolymers of butadiene, rubbery copolymers ofbutadiene and styrene, and rubbery copolymers of butadiene andacrylonitrile with (II) a partially hydrogenated organic reaction mass(0) which was thickened under acidic conditions and is normally liquidat 100 C., said (c) being (x) an organic reaction mass having aviscosity of at least 50 centipoises at 25 C. and produced by reactingunder alkaline conditions furfural and a ketone having at least 2hydrogen atoms on an alpha carbon and then hydrogenating (x) bycombining hydrogen therewith to an extent at least approximately 15% andno more than approximately 65 of that necessary to completely saturatewith hydrogen the carbon to carbon double bonds thereof the ratio byweight of (II) to (I) being no greater than 100 to 100.

4. A composition of matter comprising (I) a rubbery material selectedfrom the group consisting of natural rubber, rubbery polymers ofchloroprene, lubbery homopolymers of butadiene, rubbery copolymers ofbutadiene and styrene, and rubbery copolymers of butadiene andacrylonitrile intimately combined with (H) a partially hydrogenateddifurfuryl-ketone being difurfuryl-ketone hydrogenated to an extent atleast approximately 15% and no more than approximately 65% of thatnecessary to completely saturate with hydrogen the carbon to carbondouble bonds thereof the ratio by weight of (II) to (I) being no greaterthan 100 to 100.

5. A composition of matter comprising (1) a rubbery material selectedfrom the group consisting of natural rubber, rubbery polymers ofchloroprene, rubbery homopolymers of butadiene, rubbery copolymers ofbutadiene and styrene, and rubbery copolymers of butadiene andacrylonitrile intimately combined with (11) partially hydrogenateddifurfuryl-ketone which was thickened under acidic conditions and isnormally liquid at 100 C., said partially hydrogenated difurfuryl-ketoneproduced by hydrogenating difurfuryl-ketone to an extent at leastapproximately 15% and no more than approximately 65 of that necessary tocompletely saturate with hydrogen the carbon to carbon double bondsthereof the ratio by weight of (II) to (I) being no greater than 100 to100.

6. A composition of matter comprising (I) a rubbery polymer ofchloroprene intimately combined with (H) a partially hydrogenatedorganic reaction product normally liquid at 100 C., and selected fromthe group consisting of (a) partially hydrogenated monofurfurylketone,(b) partially hydrogenated difurfuryl-ketone, (c) partially hydrogenatedorganic reaction masses, said (0) being (x) organic reaction masseshaving a viscosity of at least 50 centipoises at 25 C. and produced byreacting under alkaline conditions furfural and a ketone having at least2 hydroatoms on an alpha carbon and then hydrogenating (x) by combininghydrogen therewith to an extent at least approximately 15 and no morethan approximately 65% of that necessary to completely saturate withhydrogen the carbon to carbon double bonds thereof, (d) partiallyhydrogenated residual fractions of (x), said (d) being residualfractions of (x) obtained by the heat distillation of (x) and measuringat least 60% of the weight of (x) and then hydrogenating said residualfractions of (x) by combining hydrogen therewith to an extent at leastapproximately 15% and no more than approximately 65% of that necessaryto completely saturate with hydrogen the carbon to carbon double bondsthereof, (2) residual fractions of (c) obtained by the heat distillationof (c) and measuring at least 60% by weight of (c), (f) polymerizedproducts produced by polymerizing (a)(e) respectively under acidicconditions, said (a) and (b) respectively produced by hydrogenatingmonofurfuryl-ketone and difurfuryl ketone by combining hydrogentherewithlo an extent at least ap-t (c) being (x) organic reactionmasses having a viscosity of at least 50 centipoises at 25 C. andproduced by reacting, under, alkaline conditions furfural and a ketonehaving at least 2 hydrogen atoms on an alpha carbon and thenhydrogenating (x) by combining hydrogen therewith to an extent at leastapproximately 15% and no more than approximately 65 of that necessary tocompletely saturate with hydrogen the carbon to carbon double bondsthereof, (d) partially hydrogenated residual fractions of (x), said (d)being residual fractions of (x) obtained by the heat distillation of (x)and measuring at least 60% of the Weight of (x) and then hydrogenatingsaid residual fractions of (x) by combining hydrogen therewith to anextent at least approximately 15% and no more than approximately 65% ofthat necessary to completely saturate with hydrogen the carbon to carbondouble bonds thereof, (a) residual fractions of obtained by the heatdistillation of (c) and measuring at least 60% by weight of (c), (f)polymerized products produced by polymerizing (a)(e) respectively underacidic conditions, said (a) and (b) respectively produced byhydrogenating monofurfuryl-ketone and difurfuryl ketone by combininghydrogen therewith to an extent at least approximately and no more thanapproximate ly 65% of that necessary to completely saturate withhydrogen the carbon to carbon double bonds thereof the ratio by Weightof (II) to (I) being no greater than 100 to 100.

8. A composition of matter comprising (I) a rubbery homopolymer ofbutadiene intimately combined with (H) a partially hydrogenated organicreaction product normally liquid at 100 C. and selected from the groupconsisting of (a) partially hydrogenated monofurfurylketone, (1))partially hydrogenated difurfuryl-ketone, (0) partially hydrogenatedorganic reaction masses, said (0) being (x) organic reaction masseshaving a viscosity of at least 50 centipoisesat C. and produced byreacting under alkaline conditions furfural and a ketone having at least2 hydrogen atoms on an alpha carbon and then hydrogenating (x) bycombining hydrogen therewith to an extent at least approximately 15% andno more than approximately 65% of that necessary to completely saturatewith hydrogen the carbon to carbon double bonds thereof, (d) partiallyhydrogenated residual fractions of (x), said (d) being residualfractions of (1') obtained by thenheat distillationlofllx) and measuringat least of.theweig ht of ;(x) and then hydrogenating said residualfractions-of, (x) by combining hydrogen therewith to an extentat leastapproximately 15% and no more than approximately-% of that necessary tocompletely saturate with hydrogen the carbon tocarbon double bondsthereof, (6) residual fractions of (0) obtained by the heat distillationof (c) and measuring at least 60% by weight of (c), (f) polymerizedproducts produced by polymerizing (u)(e)' respectively under acidicconditions, said (a) and (b) respectively produced by hydrogenatingmo'nofurfuryl-iketone and difurfuryl ketone by combining hydrogentherewith to an extent at least approximately 15 and'no more thanapproximately 65% of that necessary to, completely saturate withhydrogen the carbon to carbon double bonds thereof the ratio by weightof (ll) to (I) being no greater than to 100.

9. A composition of'matter comprising (I) a rubbery copolymer ofbutadiene and acrylonitrile intimately combined with (I I) a partiallyhydrogenated organic reaction product normally liquidat' 100 C. andselected from the 'groupconsistingof '(a) partially hydrogenatedmonofurfuryl-ketone; (b) partially hydrogenated difurfuryl-ketone, (0)partially hydrogenated organic reaction masses, said-(c) being (.11)organic'reaction masses having a viscosity of at least 50*centipoises at25 C. and produced by reacting under alkalineconditions furfural and aketone having'at-least Z'hydrogen atoms on an alpha carhon-and thenhydrogenating (x) by combining hydrogen therewith to an extent at leastapproximately 15% and no'more thntapproximately 65% of that necessary tocompletely saturate with hydrogen the carbon to carbon double bondsthereof, (a') partially hydrogenated residual fractions of: (x), said(d) being residual fractions of (.r) obtained by the heat distillationof (x) and measuring at least 60% of the weight of (x) and thenhydrogenating said residual fractions of (x) by combining hydrogentherewith to an extent at least approximately 15% and no'more thanapproximately 65 of that necessary to completely saturatetwith hydrogenthe carbon to carbondouble bonds. thereof, (2) residual fractions of (c)obtained by the'heat distillation of (c) and measuring at least 60% byweight of'(c), (f) polymerized products produced by polymerizing (a)-(e)respectively under acidic conditions, said;(a) and (b) respectivelyproduced by hydrogenating monofurfuryl-ketone and difurfuryl ketone. bycombining, hydrogen therewith to an extent at least approximately; 15%and no, more than approximately 65% of that necessary, to completelysaturate with hydrogen the'carbon to carbon double bonds thereof theratio by weight of (II) to (I) being no greater than 100 to 100.

References. Citedin the file of this patent UNITED STATES PATENTS2,190,600 Kaupp et'al Feb. 13, 1940 u no

1. A COMPOSITION OF MATTER COMPRISING (I) A MATERIAL SELECTED FROM DTHE GROUP CONSISTING OF NATURAL RUBBER, RUBBERY POLYMERS OF CHLOROPRENE, RUBBERY HOMOPOLYMERS OF BUTADIENE, RUBBERY COPOLYMERS OF BUTADIENE AND STYRENE, REBBERY COPOLYMERS OF BUTADIENE AND ACRYLONITRILE INTIMATELY COMBINED WITH (II) A PARTIALLT HYDROGEN ATED ORGANIC REACTION PRODUCT NORMALLY LIQUID AT 100*C. AND SELECTED FROM THE GROUP CONSISTING OF (A) PARTIALLY HYDROGENATED MONOFURFURYL-KETONE, (B) PARTIALLY HYDROGENATED DIFURFURYL-KETONE, (C) PARTIALLY HYDROGENATED ORGANIC REACTION MASSES, SAID (C) BEING (X) ORGANIC REACTION MASSES HAVING A VISCOSITY OF AT LEAST 5/ CENTIPOISES AT 25* C. AND PRODUCED BY REACTING UNDER ALKALINE CONDITIONS FURFURAL AND A KETONE HAVING AT LEAST 2 HYDROGEN ATOMS ON AN ALPHA CARBON AND THEN HYDROGENATING (X) BY COMBINING HYDROGEN THEREEITH TO AN EXTEND AT LEAST APPROXIMATELY 15% AND NO MORE THAN APPROXIMATELY 65% OF THAT NECESSARY TO COMPLETELY SATURATE WITH HYDROGEN THE CARBON TO CARBON DOUBLE BONDS THEREOF, (D) PARTIALLY HYDROGENATED RESIDUAL FRACTIONS OF (X), SAID (D) BEING RESIDUL FRACTIONS OF (X) OBTAINED BY THE HEAT DISTILLATION OF (X) AND MEASURING AT LEAST 60% OF THE WEIGHT OF (X) AND THEN HYDROGENATED SAID RESIDUAL FRACTIONS OF (X) BY COMBINING HUDROGEN THEREWITH TO AN EXTENT AT LEAST APPROXIMATELY 15% AND NO MORE THAN APPROXIMATELY 65% OF THAT NECESSARY TO COMPLETELY SATURATED WITH HYDROGEN THE CARBON TO CARBON DOUBLE BONDS THEREOF, (E) RESIDUAL FRACTIONS OF (C) OBTAINED BY THE HEAT DISTILLATION OF (C) AND MEASURING AT LEAST 60% BY WEIGHT OF(C), (F) POLYMERIZED PRODUCTS PRODUCED BY POLYMERIZING (A)-(E) RESPECTIVELY UNDER ACIDIC CONDITIONS, SAID (A) AND (B) RESPECTIVELY PRODUCED BY HYDROGENATING MONOFURFURYL-KETONE AND DI FURFURYL KETONE BY COMBINING HYDROGEN THEREWITH TO AN EXTENT AT LEAST APPROXIMATELT 1K% AND NO MORE THAN APPROXIMATELT 65% OF THAT NECESSARY TO COMPLETELY SATURATE WITH HYDROGEN THE CARBON TO CARBON DOUBLE BONDS THEREOF THE RATIO BY WEIGHT OF (II) TO (I) BEING NO GREATER THAN 100 TO
 100. 